JP2002003654A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JP2002003654A JP2002003654A JP2000192061A JP2000192061A JP2002003654A JP 2002003654 A JP2002003654 A JP 2002003654A JP 2000192061 A JP2000192061 A JP 2000192061A JP 2000192061 A JP2000192061 A JP 2000192061A JP 2002003654 A JP2002003654 A JP 2002003654A
- Authority
- JP
- Japan
- Prior art keywords
- radical
- rubber composition
- rubber
- weight
- containing compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 150000003254 radicals Chemical class 0.000 claims description 41
- -1 nitroxide radical Chemical class 0.000 claims description 23
- 150000001993 dienes Chemical class 0.000 claims description 4
- OHSJPLSEQNCRLW-UHFFFAOYSA-N triphenylmethyl radical Chemical compound C1=CC=CC=C1[C](C=1C=CC=CC=1)C1=CC=CC=C1 OHSJPLSEQNCRLW-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はゴム組成物に関し、
さらに詳しくは低発熱性に優れたゴム組成物に関する。The present invention relates to a rubber composition,
More specifically, it relates to a rubber composition having excellent low heat build-up.
【０００２】[0002]
【従来の技術】ゴム組成物、特にタイヤ用ゴム組成物に
おいて、タイヤなどの製品の特性を改良する種々の試み
がなされており、出願人は、特開平１０−２８２８８１
号公報、および、特開平１１−４３５５７号公報におい
て、加工性に優れ、タイヤにした場合の耐摩耗性が高
く、かつ高ウェット制動と低転動抵抗とのバランスに優
れたゴム組成物として、ラジカル化合物を配合したゴム
組成物を開示している。2. Description of the Related Art Various attempts have been made to improve the characteristics of products such as tires in rubber compositions, particularly rubber compositions for tires.
JP, JP-A-11-43557, a rubber composition having excellent workability, high wear resistance when formed into a tire, and an excellent balance between high wet braking and low rolling resistance. A rubber composition containing a radical compound is disclosed.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、地球環
境問題、省エネルギー問題から派生する自動車の低燃費
化の要求はますます強まる傾向にあり、ゴム組成物のさ
らなる低転動抵抗性、すなわち低発熱性の向上が求めら
れている。従って、本発明の課題は、低発熱性に優れた
ゴム組成物を提供することにある。However, the demand for lower fuel consumption of automobiles, which is derived from global environmental problems and energy saving problems, has been increasing more and more, and the rubber composition has further low rolling resistance, that is, low heat generation. Improvement is required. Therefore, an object of the present invention is to provide a rubber composition having excellent low heat buildup.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、少なく
とも一種のジエン系原料ゴム１００重量部に、少なくと
も一種の補強剤１０重量部以上と、少なくとも一個のイ
ソシアネート基を有するニトロキシドラジカル、ヒドラ
ジルラジカル、アリロキシルラジカル及びトリチルラジ
カルからなる群から選ばれた少なくとも一種のラジカル
を含む、常温、酸素存在下の状態において安定に存在す
るラジカル含有化合物を０．０１重量部以上、１重量部
未満配合したゴム組成物が提供される。According to the present invention, 100 parts by weight of at least one kind of diene-based raw rubber, 10 parts by weight or more of at least one kind of reinforcing agent, a nitroxide radical having at least one isocyanate group, and hydrazyl A radical-containing compound containing at least one radical selected from the group consisting of radicals, allyloxyl radicals and trityl radicals, which is stably present at room temperature and in the presence of oxygen, at least 0.01 part by weight and less than 1 part by weight A compounded rubber composition is provided.
【０００５】また、本発明によれば、前記ラジカル含有
化合物がテトラメチルピペリジニルオキシラジカルを含
む前記ゴム組成物が提供される。Further, according to the present invention, there is provided the rubber composition wherein the radical-containing compound contains a tetramethylpiperidinyloxy radical.
【０００６】また、本発明によれば、前記ラジカル含有
化合物が、ウレタン結合を有する前記ゴム組成物が提供
される。According to the present invention, there is provided the rubber composition, wherein the radical-containing compound has a urethane bond.
【０００７】さらに、本発明によれば、前記ゴム組成物
を用いたタイヤ用ゴム組成物が提供される。Further, according to the present invention, there is provided a rubber composition for a tire using the rubber composition.
【０００８】上記のように、ジエン系原料ゴム１００重
量部に、イソシアネート基を有するラジカル含有化合物
を１重量部未満とごく少量配合することにより、低発熱
性を大幅に向上させることができることを見出した。As described above, it has been found that low heat build-up can be greatly improved by blending a radical-containing compound having an isocyanate group in a very small amount of less than 1 part by weight with 100 parts by weight of a diene-based raw rubber. Was.
【０００９】[0009]
【発明の実施の形態】図１に示すように、架橋構造のゴ
ム分子（図１（ａ）参照）が光、熱、機械的にゴム分子
が切断されてラジカルが発生すると（図１（ｂ）参
照）、そのラジカルは図１（ｃ）に示すようにラジカル
含有化合物により直ちにトラップされるので、ゴム組成
物にラジカル含有化合物を配合すると、ゴム分子中にお
けるフリーラジカルの発生によるゴムの劣化や老化など
の現象を効果的に防止することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIG. 1, when a rubber molecule having a crosslinked structure (see FIG. 1 (a)) is cut by light, heat and mechanically to generate radicals (FIG. 1 (b)). )), The radicals are immediately trapped by the radical-containing compound as shown in FIG. 1 (c). Therefore, if the radical-containing compound is added to the rubber composition, the deterioration of the rubber due to the generation of free radicals in the rubber molecules and Phenomena such as aging can be effectively prevented.
【００１０】しかしながら、このようなラジカルトラッ
プによりゴムの末端の数が増加し、その結果ゴム物性が
低下する傾向にある。そこで、本発明では、カーボンブ
ラックやシリカ等の補強剤の表面の水酸基やカルボニル
基などと反応可能で、しかも反応性が非常に大きいイソ
シアネート基をラジカル含有化合物に導入することによ
って、図１（ｄ）に示すように、トラップされたゴム末
端がカーボンブラック（又はシリカ）表面と反応し、末
端の数の増加を防ぐと共に、強固なカーボンゲル（又は
シリカとのゲル）を生成しゴム物性を向上させることが
できる。However, such radical traps tend to increase the number of rubber terminals, and consequently the physical properties of the rubber tend to decrease. Therefore, in the present invention, an isocyanate group which can react with a hydroxyl group or a carbonyl group on the surface of a reinforcing agent such as carbon black or silica and has a very high reactivity is introduced into the radical-containing compound to obtain a compound shown in FIG. As shown in), the trapped rubber ends react with the surface of carbon black (or silica) to prevent an increase in the number of ends and generate a strong carbon gel (or gel with silica) to improve rubber properties. Can be done.
【００１１】ここで、ラジカル含有化合物の配合量が多
すぎると、一旦切断されたゴムの再結合が抑制され、ゴ
ムの分子量が低下しすぎるので、ゴムが補強剤に結合し
てもゴム組成物の物性が低下してしまう。If the amount of the radical-containing compound is too large, recombination of the rubber once cut is suppressed, and the molecular weight of the rubber is too low. Physical properties will be reduced.
【００１２】そこで、本発明では、このラジカル含有化
合物の配合量をごく少量とし、ゴムの分子量の過度の低
下を抑え（ゴムの再結合をあまり抑制せず）、ゴム組成
物のｔａｎδが低下し、発熱量が抑えられるという効果
を発現することが見出され、タイヤ用ゴム組成物等に低
発熱ゴム組成物として有効に利用できるということがわ
かった。また、耐摩耗性等の他の物性の向上の効果も見
出された。Therefore, in the present invention, the compounding amount of the radical-containing compound is reduced to a very small amount, so that the molecular weight of the rubber is not excessively reduced (the recombination of the rubber is not significantly suppressed), and the tan δ of the rubber composition is reduced. In addition, it has been found that the calorific value can be suppressed, and the rubber composition for tires can be effectively used as a low heat generating rubber composition. Further, the effect of improving other physical properties such as abrasion resistance was also found.
【００１３】本発明に係るゴム組成物に主成分として配
合されるゴムは従来から各種ゴム組成物に一般的に配合
されている任意のジエン系原料ゴム、例えば天然ゴム
（ＮＲ）、ポリイソプレンゴム（ＩＲ）、各種スチレン
−ブタジエン共重合体ゴム（ＳＢＲ）、各種ポリブタジ
エンゴム（ＢＲ）、アクリロニトリル−ブタジエン共重
合体ゴム（ＮＢＲ）、ブチルゴム（ＩＩＲ）などのジエ
ン系ゴムを単独又は任意のブレンドとして使用すること
ができる。The rubber compounded as a main component in the rubber composition according to the present invention may be any diene-based raw rubber conventionally compounded generally in various rubber compositions, for example, natural rubber (NR), polyisoprene rubber (IR), diene rubbers such as various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), acrylonitrile-butadiene copolymer rubbers (NBR), and butyl rubber (IIR) alone or as an arbitrary blend. Can be used.
【００１４】本発明に係るゴム組成物に配合される補強
剤としては、例えばカーボンブラック、シリカなどが挙
げられ、ジエン系ゴム１００重量部に対し、１０重量部
以上、好ましくは２０〜６０重量部配合する。この配合
量が少な過ぎるとゴム組成物として必要な補強性が得ら
れないので好ましくない。The reinforcing agent to be added to the rubber composition according to the present invention includes, for example, carbon black and silica. The reinforcing agent is at least 10 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the diene rubber. Mix. If the amount is too small, the reinforcing property required for the rubber composition cannot be obtained, which is not preferable.
【００１５】本発明に係るゴム組成物に用いられるカー
ボンブラックは、窒素比表面積（Ｎ 2ＳＡ）が好ましく
は２０〜２００ｍ2／ｇ、更に好ましくは５０〜１７０
ｍ2／ｇ、ＤＢＰ吸油量が好ましくは６０〜１３０ｍｌ
／１００ｇ、更に好ましくは８０〜１２０ｍｌ／１００
ｇである。The car used in the rubber composition according to the present invention
Bon Black has a nitrogen specific surface area (N TwoSA) is preferred
Is 20-200mTwo/ G, more preferably 50 to 170
mTwo/ G, DBP oil absorption is preferably 60 to 130 ml
/ 100g, more preferably 80-120ml / 100
g.
【００１６】本発明に係るゴム組成物に用いられるシリ
カは、ゴム配合に用いることができる任意のシリカ（又
はホワイトカーボン）とすることができ、好ましくはＮ
2ＳＡが８０〜３００ｍ2／ｇ、更に好ましくは１００〜
２５０ｍ2／ｇでＤＢＰ吸油量が１００〜３００ｍｌ／
１００ｇ、更に好ましくは１２０〜２５０ｍｌ／１００
ｇである。The silica used in the rubber composition according to the present invention can be any silica (or white carbon) that can be used in rubber compounding, and is preferably N
2 SA is 80 to 300 m 2 / g, more preferably 100 to 300 m 2 / g.
250m DBP oil absorption in the 2 / g is 100~300ml /
100 g, more preferably 120-250 ml / 100
g.
【００１７】なお、カーボンブラック及びシリカの特性
の測定方法は以下の通りである。 ａ）窒素比表面積（Ｎ2ＳＡ） ＡＳＴＭ−Ｄ３０３７−７８“Ｓｔａｎｄａｒｄ Ｍｅ
ｔｈｏｄｓ ｏｆ Ｔｒｅａｔｉｎｇ Ｃａｒｂｏｎ
Ｂｌａｃｋ−Ｓｕｒｆａｃｅ Ａｒｅａｂｙ Ｎｉｔｒ
ｏｇｅｎ Ａｄｓｏｒｐｔｉｏｎ”Ｍｅｔｈｏｄ Ｃに
よる。 ｂ）ＤＢＰ吸油量 ＡＳＴＭ−Ｄ３４９３により測定。The method of measuring the properties of carbon black and silica is as follows. a) Nitrogen specific surface area (N 2 SA) ASTM-D3037-78 “Standard Me
things of Treating Carbon
Black-Surface Area Nitr
b) DBP oil absorption Measured by ASTM-D3493.
【００１８】本発明に従えば、少なくとも一個のイソシ
アネート基を有するニトロキシドラジカル、ヒドラジル
ラジカル、アリロキシルラジカル及びトリチルラジカル
からなる群から選ばれた少なくとも一種のラジカルを含
む、常温、酸素存在下の状態において安定に存在するラ
ジカル含有化合物をジエン系ゴム１００重量部に対し
０．０１重量部以上、１重量部未満、さらに好ましく
は、０．０１重量部〜０．５重量部、特に好ましくは、
０．０１重量部以上、０．１重量部未満配合する。これ
らの配合量とすることで、本発明の低発熱性や耐摩耗性
の効果が発現される。According to the present invention, at least at room temperature and in the presence of oxygen, at least one radical selected from the group consisting of a nitroxide radical having at least one isocyanate group, a hydrazyl radical, an allyloxyl radical and a trityl radical is contained. The radical-containing compound stably present in the state is 0.01 part by weight or more and less than 1 part by weight, more preferably 0.01 part by weight to 0.5 part by weight, particularly preferably 0.01 part by weight to 100 parts by weight of the diene rubber.
0.01 to less than 0.1 part by weight is blended. By using these amounts, the effects of low heat build-up and abrasion resistance of the present invention are exhibited.
【００１９】本発明において使用することができるラジ
カル含有化合物としては、以下の化合物を例示すること
ができる。The following compounds can be exemplified as the radical-containing compound that can be used in the present invention.
【００２０】置換ニトロキシドラジカル（ピペリジニル
オキシ）（式（Ｉ）参照）Substituted nitroxide radical (piperidinyloxy) (see formula (I))
【００２１】[0021]
【化１】 Embedded image
【００２２】（式（Ｉ）中、ＲはＣ、Ｏ、Ｎ、Ｓ、Ｐ、
Ｃ1〜Ｃ30のアルキレン基及びＣ6〜Ｃ30のアリール基の
少なくとも一種又は単結合を示し、Ｒ1〜Ｒ4はそれぞれ
独立に水素又はメチル基、エチル基などのＣ1〜Ｃ4アル
キル基を示し、ｎは１〜６の整数を示す。）(In the formula (I), R is C, O, N, S, P,
At least one of a C 1 -C 30 alkylene group and a C 6 -C 30 aryl group or a single bond, and R 1 -R 4 are each independently hydrogen or a C 1 -C 4 alkyl such as a methyl group or an ethyl group; And n represents an integer of 1 to 6. )
【００２３】式（Ｉ）で示される置換ニトロキシドラジ
カル含有化合物の代表例を挙げれば、以下の通りであ
る。Typical examples of the substituted nitroxide radical-containing compound represented by the formula (I) are as follows.
【００２４】[0024]
【化２】 Embedded image
【００２５】上記の化学式のように、テトラメチルピペ
リジニルオキシラジカルを含むものが、反応性、安定
性、汎用性、経済性の点で好ましい。As described above, those containing a tetramethylpiperidinyloxy radical are preferred in terms of reactivity, stability, versatility and economy.
【００２６】また、上記の化学式のように、ウレタン結
合（−ＮＨＣＯＯ−）を有するものが、カーボンブラッ
クやシリカ等の補強剤との相溶性の向上の点で好まし
い。この傾向は、置換ニトロキシドラジカル含有化合物
以外のラジカル含有化合物についても同様である。Further, those having a urethane bond (—NHCOO—) as in the above chemical formula are preferable from the viewpoint of improving compatibility with reinforcing agents such as carbon black and silica. This tendency is the same for radical-containing compounds other than substituted nitroxide radical-containing compounds.
【００２７】置換ニトロキシドラジカル（ピロリジニル
オキシ）（式（II）又は（III）参照）Substituted nitroxide radical (pyrrolidinyloxy) (see formula (II) or (III))
【００２８】[0028]
【化３】 Embedded image
【００２９】式（II）又は式(III）で示される置換ニト
ロキシドラジカル含有化合物の代表例を挙げれば以下の
通りである。Representative examples of the substituted nitroxide radical-containing compound represented by the formula (II) or (III) are as follows.
【００３０】[0030]
【化４】 その他のニトロキシドラジカルの例として更に以下のラ
ジカル化合物の置換体も本発明のニトロキシドラジカル
含有化合物としてあげることができる。Embedded image As examples of other nitroxide radicals, further substituted compounds of the following radical compounds can be mentioned as the nitroxide radical-containing compounds of the present invention.
【００３１】[0031]
【化５】 Embedded image
【００３２】[0032]
【化６】 Embedded image
【００３３】ヒドラジルラジカルを含むラジカル含有化
合物の例としては、以下のラジカル化合物の置換体をあ
げることができる。Examples of the radical-containing compound containing a hydrazyl radical include the following substituted compounds of the radical compound.
【００３４】[0034]
【化７】 Embedded image
【００３５】アリロキシルラジカルを含むラジカル含有
化合物の例としては、以下のラジカル化合物の置換体を
あげることができる。Examples of the radical-containing compound containing an allyloxyl radical include the following substituted compounds of the radical compound.
【００３６】[0036]
【化８】 Embedded image
【００３７】トリチルラジカルを含むラジカル含有化合
物およびその類似体の例としては、以下のラジカル化合
物の置換体をできる。As examples of radical-containing compounds containing trityl radicals and analogs thereof, the following radical compounds can be substituted.
【００３８】[0038]
【化９】 Embedded image
【００３９】本発明に係るゴム組成物には、前記した必
須成分に加えて、加硫剤、架橋促進剤、各種オイル、老
化防止剤、可塑剤などのタイヤ用、その他一般ゴム用に
一般的に配合されている各種添加剤を配合することがで
き、かかる配合物は一般的な方法で混練、加硫して組成
物とし、加硫又は架橋するのに使用することができる。
これらの添加剤の配合量も本発明の目的に反しない限
り、従来の一般的な配合量とすることができる。The rubber composition according to the present invention contains, in addition to the above-mentioned essential components, a vulcanizing agent, a crosslinking accelerator, various oils, an antioxidant, a plasticizer, etc. for tires and other general rubbers. Can be blended, and such a blend can be kneaded and vulcanized into a composition by a general method, and used for vulcanization or crosslinking.
The compounding amounts of these additives can also be conventional general compounding amounts, as long as they do not contradict the object of the present invention.
【００４０】本発明のゴム組成物は、タイヤをはじめ、
コンベヤベルト、ホース、ゴムシート、手袋、防舷材等
の各種ゴム製品に適用可能であるが、タイヤとしては、
キャップトレッド、アンダートレッド等に特に好適に使
用することができる。The rubber composition of the present invention can be used for tires,
It can be applied to various rubber products such as conveyor belts, hoses, rubber sheets, gloves, fenders, etc.
It can be particularly suitably used for cap treads, under treads and the like.
【００４１】[0041]
【実施例】以下、実施例によって本発明をさらに説明す
るが、本発明の範囲をこれらの実施例に限定するもので
ないことは言うまでもない。実施例１〜４及び比較例１〜３ 表１に示す配合（重量部）において、加硫促進剤と硫黄
を除く成分を１．８リットルの密閉型ミキサーで３〜５
分間混練し、１６５±５℃に達したときに放出したマス
ターバッチに加硫促進剤と硫黄を８インチのオープンロ
ールで混練し、ゴム組成物を得た。得られたゴム組成物
を１６０℃、１０分の条件で加硫して各種試験片を作製
し、以下の各試験に供した。EXAMPLES Hereinafter, the present invention will be further described with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. Examples 1 to 4 and Comparative Examples 1 to 3 In the formulations (parts by weight) shown in Table 1, the components other than the vulcanization accelerator and sulfur were mixed in a 1.8-liter closed mixer by 3 to 5 parts.
After kneading for one minute, the masterbatch released when the temperature reached 165 ± 5 ° C. was kneaded with a vulcanization accelerator and sulfur with an 8-inch open roll to obtain a rubber composition. The obtained rubber composition was vulcanized at 160 ° C. for 10 minutes to prepare various test pieces, which were subjected to the following tests.
【００４２】３００％モジュラス（ＭＰａ） ＪＩＳ Ｋ ６２５１に準拠して測定した。ｔａｎδ 粘弾性スペクトロメーター（東洋精機（株）製）を用い
て、温度０℃及び６０℃、それぞれ、初期歪１０％、動
的歪±２％、周波数２０Hzの条件で測定した。０℃およ
び６０℃におけるｔａｎδは、値が小さいほど低発熱性
を示し、低転動抵抗性であり、良好である。耐摩耗性 ランボーン型摩耗試験機（岩本製作所製）を用いて温度
２０℃で摩耗減量を測定し、摩耗減量を指数表示した。 耐摩耗性（指数）＝〔（標準例の減量）／（サンプルの
減量）〕×１００ この指数が大きいほど、耐摩耗性が良好である。A 300% modulus (MPa) was measured according to JIS K6251. The measurement was performed using a tan δ viscoelastic spectrometer (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a temperature of 0 ° C. and 60 ° C., an initial strain of 10%, a dynamic strain of ± 2%, and a frequency of 20 Hz. The smaller the value of tan δ at 0 ° C. and 60 ° C., the lower the heat generation, the lower the rolling resistance, and the better. Wear loss was measured at a temperature of 20 ° C. using a wear-resistant Lambourn-type wear tester (manufactured by Iwamoto Seisakusho), and the wear loss was indicated as an index. Abrasion resistance (index) = [(weight loss of standard example) / (weight loss of sample)] × 100 The greater the index, the better the wear resistance.
【００４３】[0043]
【表１】 [Table 1]
【００４４】上記表１に使用した各成分は、以下のもの
を使用した。 天然ゴム：ＲＳＳ♯１ カーボンブラック：ショウブラックＮ３３９、昭和キャ
ボット社、窒素比表面積（Ｎ2ＳＡ）９２ｍ2／ｇ、ＤＢ
Ｐ吸油量１１７ｍｌ／１００ｇ ラジカル含有化合物：下記式に示される化合物The following components were used in Table 1 above. Natural rubber: RSS # 1 Carbon black: Show Black N339, Showa Cabot Co., nitrogen specific surface area (N 2 SA) 92 m 2 / g, DB
P oil absorption: 117 ml / 100 g Radical-containing compound: a compound represented by the following formula
【００４５】[0045]
【化１０】 Embedded image
【００４６】老化防止剤：Ｎ−フェニル−Ｎ’−（１，
３−ジメチルブチル）−ｐ−フェニレンジアミン 加硫促進剤：Ｎ−ｔ−ブチル−２−ベンゾチアジルスル
フェンアミドAnti-aging agent: N-phenyl-N '-(1,
3-dimethylbutyl) -p-phenylenediamine Vulcanization accelerator: Nt-butyl-2-benzothiazylsulfenamide
【００４７】上記表１に示すように、本発明のラジカル
含有化合物を０．０１重量部以上、１重量部未満配合し
た実施例１〜４は、ラジカル含有化合物を配合しなかっ
た比較例１に比べ、０℃および６０℃のｔａｎδが低下
し低発熱性が向上するうえに、耐摩耗性の改善も確認さ
れた。比較例２および比較例３は、ラジカル含有化合物
を多量に配合したものであったが、ｔａｎδは十分には
低下しなかった。As shown in Table 1 above, Examples 1 to 4 in which the radical-containing compound of the present invention was blended in an amount of 0.01 to less than 1 part by weight were compared with Comparative Example 1 in which no radical-containing compound was blended. In comparison, it was confirmed that tan δ at 0 ° C. and 60 ° C. was reduced, low heat buildup was improved, and improvement in wear resistance was also confirmed. In Comparative Examples 2 and 3, the radical-containing compound was blended in a large amount, but tan δ was not sufficiently reduced.
【００４８】[0048]
【発明の効果】本発明に従って、ゴム組成物に、少なく
とも一個のイソシアネート基を有するニトロキシドラジ
カル、ヒドラジルラジカル、アリロキシルラジカル及び
トリチルラジカルからなる群から選ばれた少なくとも一
種のラジカルを含む、常温、酸素存在下の状態において
安定に存在するラジカル含有化合物を０．０１重量部以
上、１重量部未満配合することによって、低発熱性に優
れたゴム組成物を得ることができる。According to the present invention, the rubber composition contains at least one radical selected from the group consisting of a nitroxide radical having at least one isocyanate group, a hydrazyl radical, an allyloxyl radical and a trityl radical. By blending a radical-containing compound that is stably present in the presence of oxygen in an amount of 0.01 part by weight or more and less than 1 part by weight, a rubber composition having excellent low heat build-up can be obtained.
【図１】本発明のゴム組成物におけるゴムの劣化又は老
化が防止される機能を模式的に例示した図である。FIG. 1 is a diagram schematically illustrating a function of a rubber composition of the present invention for preventing deterioration or aging of rubber.
Claims (4)
０重量部に、少なくとも一種の補強剤１０重量部以上
と、少なくとも一個のイソシアネート基を有するニトロ
キシドラジカル、ヒドラジルラジカル、アリロキシルラ
ジカル及びトリチルラジカルからなる群から選ばれた少
なくとも一種のラジカルを含む、常温、酸素存在下の状
態において安定に存在するラジカル含有化合物を０．０
１重量部以上、１重量部未満配合したゴム組成物。At least one kind of diene-based raw rubber 10
0 parts by weight contains at least 10 parts by weight of at least one reinforcing agent and at least one radical selected from the group consisting of a nitroxide radical, a hydrazyl radical, an allyloxyl radical and a trityl radical having at least one isocyanate group. A radical-containing compound stably present at room temperature in the presence of oxygen at 0.0
A rubber composition blended in an amount of 1 part by weight or more and less than 1 part by weight.
ピペリジニルオキシラジカルを含む請求項１に記載のゴ
ム組成物。2. The rubber composition according to claim 1, wherein the radical-containing compound contains a tetramethylpiperidinyloxy radical.
合を有する請求項１または２に記載のゴム組成物。3. The rubber composition according to claim 1, wherein the radical-containing compound has a urethane bond.
イヤ用ゴム組成物。4. The rubber composition for a tire according to any one of claims 1 to 3.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000192061A JP2002003654A (en) | 2000-06-27 | 2000-06-27 | Rubber composition |
| US09/859,488 US6642291B2 (en) | 2000-05-25 | 2001-05-18 | Viscoelasticity improving agent for rubber and rubber composition containing the same |
| KR1020010028605A KR20010107714A (en) | 2000-05-25 | 2001-05-24 | Viscoelasticity improving agent for rubber and rubber composition containing the same |
| DE10125578A DE10125578A1 (en) | 2000-05-25 | 2001-05-25 | Rubber viscoelasticity improving agent comprising stable lithiated free radical compound, useful in rubber compositions for producing automobile tires having reduced heat accumulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000192061A JP2002003654A (en) | 2000-06-27 | 2000-06-27 | Rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002003654A true JP2002003654A (en) | 2002-01-09 |
Family
ID=18691244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000192061A Pending JP2002003654A (en) | 2000-05-25 | 2000-06-27 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002003654A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007045273A (en) * | 2005-08-09 | 2007-02-22 | Honda Motor Co Ltd | Summer pneumatic tires |
| JP2011052189A (en) * | 2009-09-04 | 2011-03-17 | Yokohama Rubber Co Ltd:The | Rubber composition for coating steel cord |
| JP2019099816A (en) * | 2017-11-29 | 2019-06-24 | 株式会社ブリヂストン | Rubber composition for wheelchair glove and wheelchair glove |
-
2000
- 2000-06-27 JP JP2000192061A patent/JP2002003654A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007045273A (en) * | 2005-08-09 | 2007-02-22 | Honda Motor Co Ltd | Summer pneumatic tires |
| JP2011052189A (en) * | 2009-09-04 | 2011-03-17 | Yokohama Rubber Co Ltd:The | Rubber composition for coating steel cord |
| JP2019099816A (en) * | 2017-11-29 | 2019-06-24 | 株式会社ブリヂストン | Rubber composition for wheelchair glove and wheelchair glove |
| JP7501835B2 (en) | 2017-11-29 | 2024-06-18 | 株式会社ブリヂストン | Rubber composition for wheelchair gloves and wheelchair gloves |
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